2-acylaminoanthrahydroquinone compounds and process for preparing the same



2 whichlwas to beexpect d d not Occur at l I acids,ias forinstance concentrated sulfuric acid or "chlorosulfonic: acidp' It was] prev. V. inview ofjthe'rnobility 'of the acyl groups Planted 1 9 31 mam;

PATENT- o FlcE KARL scHIR c nR;- 0F HooKsT-oN-TKE-M IN, HANS SGHLICHENMAIER AND wAL'rERfKR'oss', or AJrSODEN, AND WILHELM SOHAICH; KANS'TAMPKE, AND

1 KANs N U NNQO E KsT-oN-T E-MAIN, GERMANY, ASSIGNORS TO GENERAL ANILINE woRKs, INo.,'-;oF' NEW YORK, N.1Y A CORPORATION 012 ELAW R z cxn mrnoAnrriaRAnynnooumonn comPouim's ND PRooEss FOR PREPARING j THE SAME 1 pounds'of the generalfformulaz The present invention relates A to; new com-,

- on A H I V on" f ahr ml a wa alkyl, aralkyl oraryland to a process of preparing thesame,"

,{have found @that by the} reduction of 7 2 acylaniinoanthraquinones or analogues homologues or )N-m nuclear substitution od t th f therearev exclusively o 5:10p; orlysolutiqniby m' l n fhydrogenunder V i the,presence' o f a: suitable the I said compounds I are 7; reduced in suspenp es r. and,

metallic, catalyst at a low or moderately raised tempgL-xrature,ifdesired with addition of; analkali: jTl e'f-formation of anthrones all-or only in a .yer insignificant, measure. Nor does "any hydration f of the nucleusi take I :place That rthis is theefiect of the reducfdiethers' 0r 9 .l 0-di,-lesters are easily produced tion is evident, fromthe factfthat 9.10

by etheritying or esterifying the reduction vproducts "obtained; Q In this .manner 9,10-

' dietherspr Q lO-diTestersor salts of the di- A estersulfonic acids of; 2 -acylaminoanthrahysimplest 'anthrahydroquinone isa very sen-' sitive body whichds not onlycapable of easily split anthroneontheother hand (cf. K. H. Meyer, Liebigs Annalen der Chemie, v0l.379, page sumed not: only "that the acylaminoanthra- 'hydroquinonesj behavesimilarly but. also that o aka, Mm 803- metal group or the residue of an acycliccarboxylic acid and'Z; stands for hydrogen, acyl,

Thisoccurs particularly easily in strong ew; Applicationfiled October 27,1927, Serialm.;229,2ss, and in Germany October 30,1926.

stance elimination of the acyl group and subsequent alkylation or sulfonation of the ammo -group.- When according tothe present invention a catalytic reduction is appliedhich occurs under very mild condi- I .tions, the .acyl residue is not eliminated, There are in the first place obtained the derivatives of 2-acylamino-9.lO-anthrahydroquinones which are important int-ewe;

diate productsfor the manufacture of dyestuffs and lose the'acyl group only when further treated with hot alkali. a

The following examples serve to illustrate our lnventlon; but they are notintended to limit it thereto, the parts being parts by weight. Y I

1026, 5 parts of.2 acetaminoanthraquinone of the following formula I NH-OOCH are suspended in 200 parts of alcohol, to this suspension are added 2 parts of a hydrogenatr atmospheres pressure of hydrogen. Hydrogen absorbed already at ordinary temperature w th evolution of heat and the absorption is finished after a short time. To the suspension of the easily oxidizable 2-acetaminor 9.10-anthrahydroquin0ne thus prepared are v added 25 parts of caustic soda solution of 40 B; and some water, and to this mixture are then added at ordinary temperature, while excluding air and Well stirring, 30 parts of dimethylsulfate. Heat is evolved during this reaction and it is advantageous to take care that the temperature does notexceed 40 C. The mass is keptalkaline and, if required,

some further dimethyl sulfate is added there-r to until the red color of the alkaline solution has disappeared. When the reaction finished the hitherto unknown 2-acetamino-9Ql0- anthrahydroq'uinonedimethylether of the following. formula: is j wat e r;o i ,it,is agreenislyyellow crystalline product melting in a crude state'at235P 240 9" C. and after a single crystallization ream" ailcoho'l 2117x253 0., {It dissolves; in ;a'loohol,

benzenefand glacial acetic acid to a solution 7 having a ree-n fluorescence.

ample' l the corresponding qu antity' of water;

I 4 addingbefore'hand the 25 parts ofcaustic soda tidal with that obtainable according to EX a ample '1, Inthiscase'a' clear deep-red solutio'niis obtained by the reduction. i

' 3 -26, 5 parts 2-acetaminoanthraquinone are treated; as indicated in 1Example 1; with hydrogen and a suitable nickel catalystri'n the H presence-of 200 parts'ofdry pyridine or an- "other tertiary-base as for instance dimethylaniline or'ieven', forinstance, chlorobenz ene. Hydrogen is absorbedlin a surprisingly-rapid manner-already at; ordinary temperature;

After theabsorption-of such a quantity of hydrogen as corresponds to two atomes of into mixture of 200 parts of pyridine and 60 is kept for about 1 hour; at about 6065 G.

is dbta ined; addition of potassiumchloride;

:Qlhesaid ea mm erms readily 861a 7 Whenthe' reduction occurs in" a; 'solvent like hlorobenzene, the correspdnd g anthrahyf is completely separated the addition of I 2: By using linstead O fthQ alcohol in EX;

aft-ordinary temperature as indicated in Enc aniple li a product is obtained-,[Which is idenhydrogen is finished the resulting solution or 'd suspension is slowlyrun, while excluding air,

1 parts of chlorosulfonic'facid and the whole 40 ,7 a 'Wllllfi stlrring; After cooling, the mass 1s 'pouredinto 'ice water 'a nd the precipitating pyridine salt of' the "2 acetaminoanthrahy-,

group is eliminatedand the di-potja'ssium-salt I, I

V v isfobtained' the diluted alkalinev blutioni of i'fcan lieseparated by the droquinone is precipitated. can be dis solved by the addition of pyridine. When using. 2 -formylaminoanthraquinone of the following "formula:

there is also obtained as finaf pet-duet the"? amino-anthrahydroquinone diestersulfonate.

4 265 parts'of 2-acetaminoanthraquinone are finely ground in ball mill with 'QOO'Ofparts of water, there ."are then added 228 parts of caustic soda solution Elf/235% 'strength-and the whole is reduced at room temperature by means of a catalystvconsisting of finely divided 'metallicnickel ,and10'%- of iron. The 8 dark-red solution thusfobtained is run, While stirring and excluding air; into a solution, heated to 0;, of sodium chloracetate, pre pared from 240 parts of chloracetic acid with a little water and 1&0 al-marbalcinecrsedn 6 um" carbonate; 2 temperature f is? main-a taineclfor' hour' s at 80 CL, the mass yis then "diluted with I' water; heated-to fboi'li'n g and the byproduct which? hasseparited "is filtered on in the heat. he filtrate "is' aoidifie'd by inean'l iQfjhydrochloric acid inthe c'old which causesjth ei separation of tli'eEQ' aCet-yl- H aininoanthrahydfoquinone {9;10 diaah aei d; I This facidf is isolated bydiltration and wash jtion the==2amiaoanthrahyare'qaimae alodiacetic acid ofthefollowing' formula:

which shows an intense green fluorescence.

1. 'l he process 1 which 1 comprises -.treati ng withhydrogen 2-acetylaminoanthraquinone 1 in the' p-resence of a" solventand a suitable metal-catalyst at ordinary" temperature and. "under pressure and replacing in the ;s o ;p roduced "2eacetylamino 9i10ianthrahydroqui- 3 none, the hydrogenatoms of the 9.10-OH 3 a groups by SO Me groups,Me representing 7 a metal or an organic base.

-, ZLThe. process wh'ch comprises treating 2-acetyl aminoanthraquinone in an autoclave with hydro-genin the presence of a tertiary base and a suitable nickelcatalyst at a moderate temperature under about 20 atmos I pheres pressure causing the solution thus ob-' tained containing the 2-acetylamino anthrahydroquinone to act slowly at about 30 C.

r to 60 C., while excluding air, upon a mixture of a tertiary'bas'eand the SO additio n v produ'ct thereof and converting the com-'- pound so obtained into the corresponding sodium salt byv means of sodium'carbonate.

3. The process which comprises treating 2 acetylaminoanthraquinone in an autoclave with hydrogen in the presence of pyridine and a suitable nickel. catalystat a moderate temperature under about 20 atmospheres pressure, causing the solution thus obtained 7 containing the 2-acetylaminoanthrahydroquinone'to act slowly. at about 30 C. to 60 C. while excluding'ainupon a mixture of pyridine and an addition product of pyridine and S0 and converting the compound so obtained intothe corresponding sodium salt by vmeans of sodium'carbonate.

' 4:. As a new product, thesodium .Z-acetylf aminoanthrahydroquinone-S).IO-diestersulfonate of the following formula:

' OSOsNa (IUNHooom K 'oso'sna being a saltzwhich is very readily soluble in water, yielding 'asolution having an intense V violet-blue fluorescence,splitting ofi the solution showing then a green fluorescence.

5. As new products'the compounds of the general formula;

- wherein X stands for hydrogen or the acetyl I group and R stands for CH CILCOOH or SO -metal, generally yielding solutions with a strong fluorescence;

6. As a new p-roduct,the di-potassium-2- acetyl group, whenboiled with an alkali, its

aminoanthrahydroquinone-9.10-diester sul r I fonate of the following formula:

osoix Certificate of Correction k Granted November 3, 1931, to KARL SCHIRMAGHER ET AL.

It is hereby certified that error appears in the printed specification of the abovenumbered patent requiring correction as follows: Page 1, lines 70 to 7 7, Example 1, strike out the formula and insert instead Patent No. 1,829,840.

NH.COCH

and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Oflice.

Signed and sealed this 9th day of February, A. D. 1932.

[SEAL] M. J. MOORE,

Acting Gommz'ssioner 0 f Patents. 

